JP4470370B2 - Method for manufacturing photoelectric conversion element - Google Patents

Method for manufacturing photoelectric conversion element Download PDF

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JP4470370B2
JP4470370B2 JP2003001969A JP2003001969A JP4470370B2 JP 4470370 B2 JP4470370 B2 JP 4470370B2 JP 2003001969 A JP2003001969 A JP 2003001969A JP 2003001969 A JP2003001969 A JP 2003001969A JP 4470370 B2 JP4470370 B2 JP 4470370B2
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photoelectric conversion
paste
transparent conductive
conversion element
temperature
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JP2004214129A (en
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正浩 諸岡
和宏 野田
祐輔 鈴木
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ソニー株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2068Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2027Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005Photoelectrochemical storage cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/542Dye sensitized solar cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photoelectric conversion element, a manufacturing method thereof, an electronic device, and a manufacturing method thereof, and is suitable for application to, for example, a wet solar cell using a semiconductor electrode made of semiconductor fine particles.
[0002]
[Prior art]
When fossil fuels such as coal and oil are used as an energy source, it is said that the resulting carbon dioxide causes global warming. In addition, when using nuclear energy, there is a risk of contamination by radiation. Relying on these energies is very problematic now that environmental issues are being addressed.
[0003]
On the other hand, solar cells, which are photoelectric conversion elements that convert sunlight into electrical energy, use sunlight as an energy source, and therefore have very little influence on the global environment, and are expected to become more widespread.
[0004]
There are various types of materials for solar cells, but there are many commercially available materials using silicon. These are roughly divided into crystalline silicon solar cells using single crystal or polycrystalline silicon, and amorphous ( Amorphous) and silicon-based solar cells. Conventionally, monocrystalline or polycrystalline silicon, that is, crystalline silicon, has been used in many solar cells.
[0005]
However, although the crystalline silicon solar cell has higher photoelectric conversion efficiency representing the ability to convert light (solar) energy into electric energy than the amorphous silicon solar cell, it requires much energy and time for crystal growth. Therefore, the productivity is low and the cost is disadvantageous.
[0006]
Amorphous silicon-based solar cells are more light-absorbing than crystalline silicon-based solar cells, have a wide substrate selection range, and are easy to increase in area, but have a photoelectric conversion efficiency of crystalline silicon. Lower than solar cells. Furthermore, although the productivity of amorphous silicon solar cells is higher than that of crystalline silicon solar cells, a vacuum process is required for production, and the burden on facilities is still large.
[0007]
On the other hand, many solar cells using organic materials instead of silicon-based materials have been studied for further cost reduction of solar cells. However, the photoelectric conversion efficiency of this solar cell was as low as 1% or less, and there was a problem with durability.
[0008]
Under such circumstances, Non-Patent Document 1 reported an inexpensive solar cell using porous semiconductor fine particles sensitized with a dye. This solar cell is a wet solar cell using a titanium oxide porous thin film spectrally sensitized using a ruthenium complex as a sensitizing dye as a photoelectrode, that is, an electrochemical photocell. The advantage of this solar cell is that an inexpensive oxide semiconductor such as titanium oxide can be used, the light absorption of the sensitizing dye is over a wide visible light wavelength range up to 800 nm, the quantum efficiency of photoelectric conversion is high, and high Energy conversion efficiency can be realized. Further, since no vacuum process is required for manufacturing, no large-scale equipment is required.
[Non-Patent Document 1]
Nature (353, p.737-740, 1991)
[0009]
However, since this solar cell requires a high-temperature baking process at about 500 ° C. in the process of producing a porous semiconductor electrode, it is indispensable to use a substrate that can withstand this baking temperature, and the degree of freedom in substrate selection is reduced There is a problem of doing. In this regard, many studies have been made on low-temperature firing at less than 300 ° C., as well as methods for producing a semiconductor electrode using a dry film forming method or a wet electrolytic deposition method without using a firing process. The present situation is that the semiconductor electrodes produced by these methods have poor durability, and the photoelectric conversion efficiency of solar cells remains below a few percent.
[0010]
Under these circumstances, A. Hagfeldt et al. Produced a semiconductor electrode at room temperature by applying a paste of titanium oxide fine particles containing a binder onto a substrate and then pressing the paste to press the semiconductor fine particles onto the substrate. A possible process was announced (Non-Patent Document 2).
[Non-Patent Document 2]
Journal of Photochemistry and Photobiology A: Chemistry,
145 (2001), 107
[0011]
[Problems to be solved by the invention]
According to Non-Patent Document 2, although the photoelectric conversion efficiency of the dye-sensitized solar cell in which the semiconductor electrode is produced at room temperature reaches about 4 to 5%, the solar cell in which the semiconductor electrode is produced using a firing process In comparison, the photoelectric conversion efficiency is low. In addition, according to this method, since a semiconductor electrode is produced at room temperature, a plastic substrate having low heat resistance can be used as a support for a transparent electrode. However, semiconductor fine particles formed on a plastic substrate by pressing a paste are used. The layer has low adhesion and flexibility to the substrate, and has a problem in durability against bending and stretching. In addition, ethyl cellulose is used as the binder, but this ethyl cellulose is soluble in alcohol and organic solvents, dissolves in the dye solution and electrolyte used for dye dyeing, and the characteristics deteriorate significantly over time. End up.
[0012]
  Accordingly, the problem to be solved by the present invention is a photoelectric conversion having high adhesion to a substrate of a semiconductor electrode made of semiconductor fine particles and high flexibility of the semiconductor electrode, high durability against bending and stretching, and excellent photoelectric conversion characteristics. elementManufacturing methodIs to provide.
[0014]
[Means for Solving the Problems]
As a result of various experiments and studies to solve the above-mentioned problems of the prior art, the present inventor has found that the pressing process of the paste in which the semiconductor fine particles are dispersed is performed at a higher temperature than normal temperature. The present inventors have found that it is effective for improving adhesion and flexibility to a substrate and improving photoelectric conversion efficiency, and have come up with the present invention.
[0015]
  That is, in order to solve the above problem, the first invention of the present invention is:
  Applying a paste containing semiconductor fine particles dispersed on a transparent conductive substrate, including a binder,
  After the paste is dried at a temperature not higher than the boiling point of the solvent contained in the paste to remove the solvent, the paste is pressed while being heated to a temperature not lower than 30 ° C. and not higher than the softening temperature of the transparent conductive substrate. Thus, the semiconductor fine particles are pressure-bonded onto the transparent conductive substrate to form a semiconductor electrode made of the semiconductor fine particles.
[0017]
  First of this invention2The invention of
  A paste containing semiconductor fine particles carrying a sensitizing dye and containing a binder is applied onto a transparent conductive substrate,
  After the paste is dried at a temperature equal to or lower than the boiling point of the solvent contained in the paste to remove the solvent, 30 ° C. or higher, the lower of the softening temperature of the transparent conductive substrate and the deactivation temperature of the sensitizing dye A method for producing a photoelectric conversion element, wherein the semiconductor fine particles are pressed onto the transparent conductive substrate by pressing the paste while being heated to a temperature equal to or lower than that temperature to form a semiconductor electrode composed of the semiconductor fine particles. It is.
[0019]
In this invention, the temperature at which the dried paste is pressed is preferably 40 ° C. or higher, more preferably 50 ° C. or higher in order to sufficiently improve the adhesion and flexibility of the semiconductor electrode to the substrate. On the other hand, when a transparent plastic substrate is used as a support for the transparent conductive substrate, or when a sensitizing dye is previously supported on semiconductor fine particles dispersed in a paste, the transparent conductive substrate and sensitizing dye to be used are also used. However, the upper limit of the temperature during the pressing is generally 150 to 200 ° C. The temperature during the pressing is typically 50 ° C. or higher and 120 ° C. or lower. The paste is dried to remove the solvent contained in the paste, and the drying temperature is not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is about 50 ° C., and when the solvent is an organic solvent, the temperature is about 100 ° C. It is common.
[0020]
There is no particular limitation on the paste pressing method, and various methods such as a press molding method using a flat plate press, a roll pressing method using a roll or the like, and a rolling (calendar) method can be used. There is no upper limit to the pressure applied to the paste at the time of pressing, but when a high pressure is applied, the adhesion of the semiconductor fine particle layer to the substrate is increased, so that a photoelectric conversion element having excellent durability can be realized. This pressure is usually 500 kg / cm2Or more, preferably 1000 kg / cm2Or more, preferably 5000 kg / cm2That's it. The time for heating and pressing is not particularly limited, but is usually about 1 second to 600 seconds, and preferably 3 seconds to 300 seconds in consideration of productivity and adhesion of the semiconductor fine particle layer.
[0021]
The transparent conductive substrate may be one in which a transparent conductive film is formed on a conductive or non-conductive transparent support substrate, or the whole may be a conductive transparent substrate. The material in particular of this transparent support substrate is not restrict | limited, A various base material can be used if it is transparent. This transparent support substrate is preferably one that is excellent in moisture and gas barrier properties, solvent resistance, weather resistance, etc. entering from the outside of the photoelectric conversion element, specifically, transparent inorganic substrates such as quartz and glass, polyethylene Terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, tetraacetylcellulose, brominated phenoxy, aramids, polyimides, polystyrenes, polyarylates, polysulfones, polyolefins, etc. Although a transparent plastic substrate is mentioned, it is not limited to these. As this transparent support substrate, it is preferable to use a transparent plastic substrate in consideration of processability, lightness and the like. Further, the thickness of the transparent support substrate is not particularly limited, and can be freely selected depending on the light transmittance, the shielding property between the inside and outside of the photoelectric conversion element, and the like.
[0022]
The lower the surface resistance of the transparent conductive substrate, the better. Specifically, the surface resistance of the transparent conductive substrate is preferably 500Ω / □ or less, and more preferably 100Ω / □. In the case of forming a transparent conductive film on a transparent support substrate, a known material can be used as the material, specifically, indium-tin composite oxide (ITO), fluorine-doped SnO.2(FTO), SnO2However, the present invention is not limited to these, and two or more of these can be used in combination. In addition, for the purpose of reducing the surface resistance of the transparent conductive substrate and improving the current collection efficiency, it is also possible to pattern a highly conductive metal wiring on the transparent conductive substrate.
[0023]
As a material for the semiconductor fine particles, various compound semiconductors, compounds having a perovskite structure, and the like can be used in addition to elemental semiconductors typified by silicon. These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and give an anode current. These semiconductors are specifically exemplified by TiO.2, ZnO, WOThree, Nb2OFiveTiSrOThree, SnO2Of these, TiO2Is particularly preferred. Moreover, the kind of semiconductor is not limited to these, It can also be used in mixture of 2 or more types.
[0024]
Although there is no restriction | limiting in particular in the particle size of semiconductor fine particle, 1-200 nm is preferable at the average particle diameter of a primary particle, Most preferably, it is 5-100 nm. It is also possible to improve the quantum yield by mixing semiconductor fine particles having an average particle size larger than the average particle size into semiconductor fine particles having an average particle size and scattering incident light by the semiconductor fine particles having a large average particle size. is there. In this case, the average particle diameter of the semiconductor fine particles to be mixed separately is preferably 20 to 500 nm.
[0025]
There is no particular limitation on the method for producing the paste containing the semiconductor fine particles dispersed, including the binder, but in view of physical properties, convenience, production cost, etc., the wet film forming method is preferable, and the powder or sol of the semiconductor fine particles is used. A method of uniformly dispersing in a solvent such as water and further adding a binder to prepare a paste and applying the paste on a transparent conductive substrate is preferable. The coating method is not particularly limited and can be performed according to a known method. For example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or a wet printing method. Can be performed by various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing. When crystalline titanium oxide is used as the material for the semiconductor fine particles, the anatase type is preferable from the viewpoint of photocatalytic activity. The anatase-type titanium oxide may be a commercially available powder, sol, or slurry, or may be made with a predetermined particle diameter by a known method such as hydrolysis of titanium oxide alkoxide. When using a commercially available powder, it is preferable to eliminate secondary aggregation of the particles, and it is preferable to pulverize the particles using a mortar, ball mill or the like when preparing the coating solution. At this time, acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, or the like can be added in order to prevent the particles whose secondary aggregation has been released from aggregating again.
[0026]
It is preferable that the binder added to the paste is insoluble in the dye solution and the electrolytic solution at the time of dyeing. Known binders can be used, and celluloses, polyethers, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polyethyleneimine, methyl poly (meth) acrylate, polyvinylidene fluoride. , Styrene butadiene rubber, polyamideimide, polytetrafluoroethylene (fluororesin), and the like, but are not limited to these, and two or more kinds may be used in combination.
[0027]
In general, as the thickness of the semiconductor fine particle layer increases, the amount of the supported dye increases per unit projected area and thus the light capture rate increases. However, the diffusion distance of injected electrons increases and the loss due to charge recombination also increases. . Accordingly, a preferable thickness exists in the semiconductor fine particle layer, but the thickness is generally 0.1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 3 to 30 μm. . In order to increase the thickness of the semiconductor fine particle layer, it is also possible to stack the semiconductor fine particle layer by applying the paste again on the semiconductor fine particle layer once press-molded and pressing the paste again. In order to increase the surface area of semiconductor fine particles, remove impurities in the semiconductor fine particle layer, and increase the efficiency of electron injection from the dye to the semiconductor fine particles, for example, chemical plating using titanium tetrachloride aqueous solution or electricity using titanium trichloride aqueous solution Chemical plating may be performed. In addition, a conductive additive may be added for the purpose of reducing the impedance of the semiconductor fine particle layer.
[0028]
The dye to be carried on the semiconductor fine particles is not particularly limited as long as it exhibits a sensitizing action. , Basic dyes such as phenosafranine, foggy blue, thiocin, methylene blue, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, other azo dyes, phthalocyanine compounds, coumarin compounds, Ru bipyridine complex compounds, anthraquinone dyes, many And ring quinone dyes. Among these, a ruthenium (Ru) bipyridine complex compound is particularly preferable because of its high quantum yield, but is not limited thereto, and can be used alone or in combination of two or more.
[0029]
There is no particular limitation on the method for supporting the dye on the semiconductor fine particle layer. For example, the dye may be an alcohol, nitrile, nitromethane, halogenated hydrocarbon, ether, dimethyl sulfoxide, amide, N-methylpyrrolidone, 1, 3 -Dissolve in a solvent such as dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, water, etc., soak the semiconductor fine particle layer, or apply a dye solution to the semiconductor fine particle layer The method to do is common. Further, it is more preferable to dissolve the dye in a paste in which semiconductor fine particles are dispersed, and apply and press-mold semiconductor fine particles in which the dye is previously supported. In this case, the charged amount of the dye molecules with respect to one semiconductor fine particle is 1-1000 molecules, and more preferably 1-100 molecules. In addition, when the dye molecules are supported in a large excess with respect to the semiconductor fine particles, electrons excited by light energy are not injected into the semiconductor fine particles, which causes an energy loss because the electrolyte is reduced. Therefore, the dye molecule is in an ideal state of single molecule adsorption with respect to the semiconductor fine particles, and the temperature and pressure to be supported can be changed as necessary. Carboxylic acids such as deoxycholic acid may be added for the purpose of reducing association between the dyes. An ultraviolet absorber can also be used in combination.
[0030]
For the purpose of accelerating the removal of the excessively supported dye, the surface of the semiconductor fine particle layer supporting the dye may be treated with amines. Examples of amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquids, they may be used as they are, or may be used after being dissolved in an organic solvent.
[0031]
Any material can be used as the counter electrode as long as it is a conductive material, but an insulating material can also be used as long as a conductive layer is provided on the side facing the semiconductor electrode. However, an electrochemically stable material is preferably used as the electrode, and specifically, platinum, gold, carbon, and the like are preferably used. For the purpose of improving the catalytic effect of redox, it is preferable that the side facing the semiconductor electrode has a fine structure and the surface area is increased. It is desired to be in a porous state. The platinum black state can be formed by platinum anodic oxidation method, chloroplatinic acid treatment, and the like, and the porous carbon can be formed by methods such as sintering of carbon fine particles and organic polymer firing.
[0032]
The electrolyte is iodine (I2) And metal iodide or organic iodide, bromine (Br2) And metal bromide or organic bromide, metal complexes such as ferrocyanate / ferricyanate and ferrocene / ferricinium ions, sulfur compounds such as sodium polysulfide, alkylthiol / alkyl disulfide, viologen dyes, Hydroquinone / quinone or the like can be used. As the cation of the metal compound, Li, Na, K, Mg, Ca, Cs and the like, and as the cation of the organic compound, a quaternary ammonium compound such as tetraalkylammoniums, pyridiniums and imidazoliums is preferable. However, the present invention is not limited to these, and two or more of these can be used in combination. Among these, I2An electrolyte combining quaternary ammonium compounds such as LiI, NaI and imidazolium iodide is suitable. The concentration of the electrolyte salt is preferably 0.05M to 5M, more preferably 0.2M to 1M, with respect to the solvent. I2And Br2The concentration of is preferably 0.0005M to 1M, more preferably 0.0001 to 0.1M. Various additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open circuit voltage and the short circuit current.
[0033]
Water, alcohols, ethers, esters, carbonate esters, lactones, carboxylic acid esters, phosphoric acid triesters, heterocyclic compounds, nitriles, ketones, amides as a solvent constituting the electrolyte composition Nitromethane, halogenated hydrocarbons, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbons, etc., but are not limited thereto, It can be used alone or in combination of two or more. Further, a room temperature ionic liquid of a tetraalkyl, pyridinium, or imidazolium quaternary ammonium salt can be used as a solvent.
[0034]
For the purpose of reducing leakage of the photoelectric conversion element and volatilization of the electrolyte, it is possible to dissolve the gelling agent, polymer, cross-linking monomer, etc. in the above electrolyte composition and use it as a gel electrolyte. As for the ratio between the gel matrix and the electrolyte composition, the more the electrolyte composition, the higher the ionic conductivity, but the lower the mechanical strength. On the other hand, if the electrolyte composition is too small, the mechanical strength is large but the ionic conductivity is lowered. Therefore, the electrolyte composition is desirably 50 wt% to 99 wt% of the gel electrolyte, and more preferably 80 wt% to 97 wt%. It is also possible to realize an all-solid-type photoelectric conversion element by dissolving it in a polymer using the electrolyte and the plasticizer and volatilizing and removing the plasticizer.
[0035]
The manufacturing method of the photoelectric conversion element is not particularly limited, but for example, the electrolyte composition can be liquid or gelled inside the photoelectric conversion element, and in the case of a liquid electrolyte composition before introduction, the semiconductor electrode and the counter electrode The substrate portion where the semiconductor electrode is not formed is sealed so that the two electrodes are not in contact with each other. At this time, although there is no restriction | limiting in particular in the clearance gap between a semiconductor electrode and a counter electrode, Usually, it is 1-100 micrometers, More preferably, it is 1-50 micrometers. If the distance between the electrodes is too long, the photocurrent decreases due to the decrease in conductivity. The sealing method is not particularly limited, but a material having light resistance, insulation, and moisture resistance is preferable. Various welding methods, epoxy resins, ultraviolet curable resins, acrylic adhesives, EVA (ethylene vinyl acetate), ionomers Resins, ceramics, heat fusion films, and the like can be used. Moreover, although the injection port which injects the solution of electrolyte composition is required, if it is not on the counter electrode of a semiconductor electrode layer and the part facing it, the place of an injection port will not be specifically limited. Although there is no restriction | limiting in particular in the liquid injection method, The method of injecting into the inside of the said cell sealed beforehand and opened the injection port of the solution is preferable. In this case, a method of dropping a few drops of the solution at the injection port and injecting the solution by capillary action is simple. In addition, the injection operation can be performed under reduced pressure or under heating as necessary. After the solution is completely injected, the solution remaining at the inlet is removed and the inlet is sealed. Although there is no restriction | limiting in particular also in this sealing method, If necessary, it can also seal by sticking a glass plate or a plastic substrate with a sealing agent. In the case of a gel electrolyte using a polymer or the like, or an all solid electrolyte, a polymer solution containing an electrolyte composition and a plasticizer is volatilized and removed on a semiconductor electrode carrying a dye by a casting method. After completely removing the plasticizer, sealing is performed in the same manner as in the above method. This sealing is preferably performed using a vacuum sealer or the like under an inert gas atmosphere or under reduced pressure. After sealing, in order to sufficiently impregnate the electrolyte into the semiconductor fine particle layer, heating and pressurizing operations can be performed as necessary.
The photoelectric conversion element can be manufactured in various shapes depending on the application, and the shape is not particularly limited.
[0042]
  According to the present invention configured as described above,A paste containing semiconductor fine particles containing a binder or a paste containing semiconductor fine particles carrying a sensitizing dye containing a binder is applied onto a transparent conductive substrate, and the paste is contained in the paste. After removing the solvent by drying at a temperature not higher than the boiling point of the solvent, the temperature is not lower than 30 ° C. and not higher than the softening temperature of the transparent conductive substrate, or the softening temperature of the transparent conductive substrate and the deactivation temperature of the sensitizing dye. By pressing the paste while heating to a temperature lower than the lower temperature, the semiconductor fine particles are pressed onto the transparent conductive substrate to be composed of the semiconductor fine particles.By forming the semiconductor electrode, the semiconductor electrodeTransparent conductivityThe adhesion and flexibility to the substrate can be improved, and the durability of the semiconductor electrode against bending and bending can be improved.
[0043]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 shows a dye-sensitized wet photoelectric conversion device according to an embodiment of the present invention.
As shown in FIG. 1, in this dye-sensitized wet photoelectric conversion device, a transparent conductive substrate 1 on which a semiconductor fine particle layer 2 (semiconductor electrode) carrying a sensitizing dye is formed, and a transparent conductive substrate 3 having platinum or a platinum catalyst layer 4 formed thereon is disposed so that the semiconductor fine particle layer 2 and the platinum or platinum catalyst layer 4 face each other at a predetermined interval. An electrolyte layer (electrolytic solution) 5 is sealed in the space. The electrolyte layer 5 is sealed with a predetermined sealing member (not shown). Here, the semiconductor fine particle layer 2 is formed by press-bonding a paste containing semiconductor fine particles containing a binder and preliminarily supporting sensitizing dyes by a press.
[0044]
In FIG. 2, in particular, the transparent conductive substrate 1 has a transparent electrode 1b formed on a transparent substrate 1a, and the transparent conductive substrate 3 has a transparent electrode 3b formed on a transparent substrate 3a. 1 shows a dye-sensitized wet photoelectric conversion element.
[0045]
The transparent conductive substrate 1 (or the transparent substrate 1a and the transparent electrode 1b), the semiconductor fine particle layer 2, the transparent conductive substrate 3 (or the transparent substrate 3a and the transparent electrode 3b) and the electrolyte layer 5 can be selected from those already mentioned. It can be selected as needed.
[0046]
Next, the manufacturing method of this dye-sensitized wet photoelectric conversion element is demonstrated.
That is, first, the transparent conductive substrate 1 is prepared. Next, as shown in FIG. 3A, a paste 6 in which semiconductor fine particles carrying a sensitizing dye and containing a binder are dispersed is applied to the transparent conductive substrate 1 in a predetermined gap (thickness). . Next, the paste 6 is heated while being heated to 30 ° C. or higher, the lower one of the softening temperature of the transparent conductive substrate 1 and the deactivation temperature of the sensitizing dye, preferably 50 ° C. to 120 ° C. Is pressed by a predetermined method and pressure. This pressure is 500 kg / cm2Or more, preferably 5000 kg / cm2More than 20000 kg / cm2It is as follows. By this heating press, as shown in FIG. 3B, the dye-carrying semiconductor fine particle layer 2 is formed on the transparent conductive substrate 1 by pressure bonding.
[0047]
On the other hand, a separate transparent conductive substrate 3 is prepared, and platinum or a platinum catalyst layer 4 is formed thereon.
The transparent conductive substrate 1 and the transparent conductive substrate 3 are separated from each other by a predetermined distance, for example, 1 to 100 μm, preferably 1 to 50 μm, between the semiconductor fine particle layer 2 and the platinum or platinum catalyst layer 4. And a space for enclosing the electrolyte layer 5 using a predetermined sealing member, and the electrolyte layer 5 is injected from a liquid injection port formed in advance in this space. Thereafter, the liquid injection port is closed. Thereby, a dye-sensitized wet photoelectric conversion element is manufactured.
[0048]
Next, operation | movement of this dye-sensitized wet photoelectric conversion element is demonstrated.
The light incident through the transparent conductive substrate 1 from the transparent conductive substrate 1 side excites the sensitizing dye carried on the surface of the semiconductor fine particle layer 2 to generate electrons. The electrons are quickly transferred from the sensitizing dye to the semiconductor fine particles of the semiconductor fine particle layer 2. On the other hand, the sensitizing dye that has lost the electrons receives electrons from the ions of the electrolyte layer 5, and the molecule that has passed the electrons receives the electrons again at the counter platinum or platinum catalyst layer 4. Through this series of processes, an electromotive force is generated between the transparent conductive substrate 1 electrically connected to the semiconductor fine particle layer 2 and the transparent conductive substrate 3 electrically connected to the platinum or platinum catalyst layer 4. To do. In this way, photoelectric conversion is performed.
[0049]
As described above, according to this embodiment, 30 ° C. or higher, the lower one of the softening temperature of the transparent conductive substrate 1 and the deactivation temperature of the sensitizing dye, preferably 50 ° C. or higher and 120 ° C. or lower. The semiconductor fine particle layer 2 is pressed and formed on the transparent conductive substrate 1 by pressing the paste 6 in which the semiconductor fine particles previously loaded with the sensitizing dye containing the binder are dispersed while being heated to the temperature of The adhesion and flexibility of the semiconductor fine particle layer 2 to the substrate can be improved, whereby the durability against the bending and expansion / contraction of the semiconductor fine particle layer 2 is increased, and the photoelectric conversion efficiency is sufficiently high. For this reason, the dye-sensitized wet photoelectric conversion element excellent in durability and a photoelectric conversion characteristic, especially a dye-sensitized wet solar cell are realizable. Moreover, since this dye-sensitized wet photoelectric conversion element can be manufactured without using a high-temperature baking process, the degree of freedom in selecting a substrate material is high.
[0050]
【Example】
Examples of the dye-sensitized wet photoelectric conversion element will be described. The conditions of the examples are summarized in Table 1. The measurement results of the examples are shown in Table 2 together with the measurement results of the comparative example.
[Table 1]
[Table 2]
[0051]
Example 1
TiO as semiconductor fine particles2Fine particles were used. TiO containing binder2A paste in which fine particles were dispersed was prepared as follows with reference to Hironori Arakawa “Latest Dye-Sensitized Solar Cell Technology” (CMC) p.45-47 (2001). 125 ml of titanium isopropoxide was slowly added dropwise to 750 ml of 0.1 M nitric acid aqueous solution with stirring at room temperature. When the dropping was completed, this solution was transferred to a constant temperature bath at 80 ° C. and stirred for 8 hours to obtain a cloudy translucent sol solution. The sol solution was allowed to cool to room temperature, filtered through a glass filter, and then made up to 700 ml. The obtained sol solution was transferred to an autoclave, hydrothermally treated at 220 ° C. for 12 hours, and then subjected to dispersion treatment by performing ultrasonic treatment for 1 hour. The solution is then concentrated with an evaporator at 40 ° C.2The content was adjusted so as to be 20 wt%. To this concentrated sol solution, the TiO in the paste2Hydroxyethyl cellulose was added so that it might become 5 wt% with respect to the weight of the TiO2, and it mixed uniformly with the planetary ball mill, and was thickened TiO2A paste was obtained.
[0052]
This TiO2To the paste, cis-bis (isothiocyanate) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) dihydrate is added with 1 TiO.2TiO 2 is dissolved at a charge ratio of 10 molecules with respect to fine particles.2The dye was adsorbed on the fine particles.
[0053]
Obtained dye-supported TiO2The paste is blade coated and the surface is SnO2After coating with a conductive PET substrate (sheet resistance 50Ω / □) with a size of 1 cm × 1 cm and a gap of 200 μm, 120 ° C. and 10,000 kg / cm using a press molding machine.2Crimping was performed for 30 seconds under the conditions described above. Dye-supported TiO formed by pressure bonding in this way2On the fine particle layer, the above dye-supported TiO with a gap of 200 μm.2The paste is blade coated and dye-supported TiO under the same conditions as above2A fine particle layer was formed by pressure bonding.
[0054]
The counter electrode has a surface of SnO with a 1 mm injection hole previously opened.2A conductive PET substrate (sheet resistance: 50Ω / □) coated with a platinum sputtered with a thickness of 100 nm was used.
Dye-supported TiO formed as described above2The fine particle layer, that is, the semiconductor electrode and the platinum surface of the counter electrode face each other, and the outer periphery thereof was sealed with an EVA film having a thickness of 30 μm and an epoxy adhesive.
[0055]
Meanwhile, 3 g of methoxypropionitrile, 0.04 g of lithium iodide (LiI), 0.479 g of 1-propyl-2,3-dimethylimidazolium iodide, iodine (I2) 0.0381 g and 4-tert-butylpyridine 0.2 g were dissolved to prepare a mixed solution to prepare an electrolyte composition.
[0056]
After dropping a few drops of the above electrolyte composition into the liquid injection port formed in advance as described above and reducing the pressure, the liquid injection port was sealed with an EVA film, an epoxy adhesive, and a PET substrate. Then, a dye-sensitized wet photoelectric conversion element was obtained.
[0057]
Examples 2-6
A dye-sensitized wet photoelectric conversion element was produced in the same manner as in Example 1 except that the paste was pressed under the conditions shown in Table 1.
[0058]
Example 7
TiO prepared as in Example 12The surface of the paste is SnO by the blade coating method.2After coating with a conductive PET substrate (sheet resistance 50Ω / □) with a size of 1 cm × 1 cm and a gap of 200 μm, it is 120 ° C. and 10,000 kg / cm by a press molding machine.2Crimping was performed for 30 seconds under the conditions described above. Dye-supported TiO formed by pressure bonding in this way2On the fine particle layer, the above dye-supported TiO with a gap of 200 μm.2The paste is blade coated and dye-supported TiO under the same conditions as above2A fine particle layer was formed by pressure bonding.
[0059]
Then 0.5 mM cis-bis (isothiocyanate) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) dihydrate and 20 mM deoxychol Immerse in dehydrated ethanol solution in which acid is dissolved for 12 hours,2A dye was supported on the fine particle layer. The dye-supported TiO thus obtained2The fine particle layer was washed with an ethanol solution of 4-tert-butylpyridine and dehydrated ethanol in this order, and dried in a dark place.
The assembly of the photoelectric conversion element and the adjustment of the electrolyte composition were performed in the same manner as in Example 1.
[0060]
Examples 8-12
A dye-sensitized wet photoelectric conversion element was produced in the same manner as in Example 10 except that the paste was pressed under the conditions shown in Table 1.
[0061]
Examples 13-19
A dye-sensitized wet photoelectric conversion element was produced in the same manner as in Example 1 except that the binder shown in Table 1 was used.
[0062]
Example 20
TiO prepared as in Example 12After the concentrated sol solution is dried with an evaporator and a vacuum dryer, TiO220 wt%, polyvinylidene fluoride 1 wt% and N-methylpyrrolidone 79 wt% were mixed in a planetary ball mill, and TiO2A paste was prepared.
The method for supporting the dye, press molding, assembly of the photoelectric conversion element, and adjustment of the electrolyte composition were performed in the same manner as in Example 1.
[0063]
Examples 21-22
A dye-sensitized wet photoelectric conversion element was produced in the same manner as in Example 20 except that the binder shown in Table 1 was used.
[0064]
Example 23
Using a fluorine-doped conductive glass substrate (sheet resistance 10Ω / □) as a transparent conductive substrate, platinum is applied to a fluorine-doped conductive glass substrate (sheet resistance 10Ω / □) with a 1 mm injection hole previously opened in the counter electrode. Dye-sensitized wet photoelectric conversion element in the same manner as in Example 1 except that a 100 nm-thick sputter, a few drops of an ethanol solution of chloroplatinic acid were dropped thereon, heated to 385 ° C. and treated with platinum chloride were used. Was made.
[0065]
Comparative Examples 1-6
A dye-sensitized wet photoelectric conversion device was produced in the same manner as in Example 1 except that the paste was pressed under the conditions shown in Table 1 (at room temperature).
Comparative Example 7
TiO prepared in Example 12Polyethylene glycol (PEG) with a molecular weight of 500,000 is added to the concentrated sol solution, mixed uniformly with a planetary ball mill, and thickened TiO2A paste was obtained.
Obtained TiO2The paste was applied to a fluorine-doped conductive glass substrate (sheet resistance 10Ω / □) by a blade coating method with a size of 1 cm × 1 cm and a gap of 200 μm, and held at 450 ° C. for 30 minutes, and TiO 22Was sintered onto a conductive glass substrate.
[0066]
Then 0.5 mM cis-bis (isothiocyanate) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) dihydrate and 20 mM deoxychol Immerse in dehydrated ethanol solution in which acid is dissolved for 12 hours,2The dye was adsorbed on the fine particles. The dye-supported TiO thus obtained2The fine particle layer was washed with an ethanol solution of 4-tert-butylpyridine and dehydrated ethanol in this order, and dried in a dark place.
[0067]
The counter electrode was formed by sputtering platinum with a thickness of 100 nm onto a fluorine-doped conductive glass substrate (sheet resistance 10 Ω / □) having a 1 mm injection hole previously opened, and dropping a few drops of an ethanol solution of chloroplatinic acid on it. The one treated with platinum chloride by heating to ℃ was used.
Dye-supported TiO formed as described above2The fine particle layer and the platinum surface of the counter electrode face each other, and the outer periphery thereof was sealed with an EVA film having a thickness of 30 μm and an epoxy adhesive.
[0068]
On the other hand, 3 g of methoxypropionitrile was added to 0.04 g of lithium iodide (LiI), 0.479 g of 1-propyl-2,3-dimethylimidazolium iodide, iodine (I2) 0.0381 g and 4-tert-butylpyridine 0.2 g were dissolved to prepare a mixed solution to prepare an electrolyte composition.
After dropping a few drops of the above electrolyte composition into the liquid injection port formed in advance as described above and reducing the pressure, the liquid injection port was sealed with an EVA film, an epoxy adhesive, and a PET substrate. Then, a dye-sensitized wet photoelectric conversion element was obtained.
[0069]
Comparative Example 8
TiO2A dye-sensitized wet photoelectric conversion element was produced in the same manner as in Comparative Example 1 except that the firing temperature was 150 ° C.
[0070]
Comparative Example 9
SnO on the surface of a transparent conductive substrate2Using a conductive PET substrate (sheet resistance 50 Ω / □) coated with, a 1 mm injection hole was previously opened on the counter electrode, and the surface was SnO2A dye-sensitized wet photoelectric conversion device was produced in the same manner as in Comparative Example 8 except that a conductive PET substrate (sheet resistance 50 Ω / □) coated with a platinum was used to sputter platinum with a thickness of 100 nm.
[0071]
In the dye-sensitized wet photoelectric conversion elements of Examples 1 to 23 and Comparative Examples 1 to 9 produced as described above, simulated sunlight (AM1.5, 100 mW / cm2) Photoelectric conversion efficiency at the time of irradiation was measured every month until 3 months later. For a transparent conductive substrate using a plastic substrate as a support, during the measurement period, the light receiving surface side of the photoelectric conversion element faces outward and remains curved at a curvature of 1/5 mm at room temperature in a dark place Saved in. Those using a glass substrate as the support were stored in the dark at room temperature.
[0072]
Among the photoelectric conversion elements, a curved one is TiO.2The state of the fine particle layer was visually confirmed. The above measurement results are shown in Table 2.
From Table 2, the photoelectric conversion efficiency of the dye-sensitized wet photoelectric conversion elements according to Examples 1 to 23 is equivalent to that of the dye-sensitized wet photoelectric conversion elements according to Comparative Examples 7 to 9 using a conventional baking process. Compared with the low temperature firing process, the characteristics are far superior. It can also be seen that even when bent using a plastic substrate, cracking and peeling do not occur and the durability is excellent. Furthermore, the dye-sensitized wet photoelectric conversion elements according to Examples 1 to 23 are superior in photoelectric conversion efficiency and durability as compared with the dye-sensitized wet photoelectric conversion elements according to Comparative Examples 1 to 6 that were pressed at room temperature. I understand that.
[0073]
Although one embodiment of the present invention has been specifically described above, the present invention is not limited to the above-described embodiment, and various modifications based on the technical idea of the present invention are possible.
For example, the numerical values, structures, shapes, materials, raw materials, processes, and the like given in the above-described embodiments are merely examples, and numerical values, structures, shapes, materials, raw materials, processes, etc. different from these are used as necessary. Also good.
[0074]
Specifically, for example, in the above-described embodiment, a paste in which a sensitizing dye is previously supported on semiconductor fine particles is applied, but after applying a paste in which a sensitizing dye is not supported on semiconductor fine particles, The applied paste may be dyed so that the semiconductor fine particles in the paste carry the dye.
[0075]
【The invention's effect】
As described above, according to the present invention, a paste containing a binder and containing dispersed semiconductor fine particles is applied onto a transparent conductive substrate, and after the paste is dried, the transparent conductive substrate is heated to 30 ° C. or higher. The semiconductor fine particles are made transparent by pressing this paste while heating to a temperature lower than the softening temperature of the transparent conductive substrate or the lower temperature of the softening temperature of the transparent conductive substrate and the deactivation temperature of the sensitizing dye. By forming a semiconductor electrode by pressure bonding on a conductive substrate, a photoelectric conversion element having high adhesion and flexibility to the substrate of the semiconductor electrode, high durability against bending and expansion and contraction, and excellent photoelectric conversion characteristics is obtained. Can do.
[0076]
According to the present invention, the paste containing the binder and containing the semiconductor fine particles is applied on the substrate, and after the paste is dried, the temperature is 30 ° C. or more and the substrate softening temperature or less, or the substrate By pressing this paste while heating to a temperature lower than the lower one of the softening temperature and the deactivation temperature of the sensitizing dye, the semiconductor fine particles are pressed onto the substrate to form a semiconductor electrode. An electronic device having high adhesion and flexibility to the substrate of the electrode, high durability against bending and expansion / contraction, and excellent characteristics such as photoelectric conversion characteristics can be obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a main part of a dye-sensitized wet photoelectric conversion device according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a main part of a dye-sensitized wet photoelectric conversion device according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view for explaining a method for producing a dye-sensitized wet photoelectric conversion device according to an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Transparent conductive substrate, 1a ... Transparent substrate, 1b ... Transparent electrode, 2 ... Semiconductor fine particle layer, 3 ... Transparent conductive substrate, 3a ... Transparent substrate, 3b ... Transparent electrode, 4 ... Platinum or platinum catalyst layer, 5 ... Electrolyte layer

Claims (9)

  1. Applying a paste containing semiconductor fine particles dispersed on a transparent conductive substrate, including a binder,
    After the paste is dried at a temperature not higher than the boiling point of the solvent contained in the paste to remove the solvent, the paste is pressed while being heated to a temperature not lower than 30 ° C. and not higher than the softening temperature of the transparent conductive substrate. A method for producing a photoelectric conversion element, wherein the semiconductor fine particles are pressure-bonded onto the transparent conductive substrate to form a semiconductor electrode composed of the semiconductor fine particles.
  2.   The method for producing a photoelectric conversion element according to claim 1, wherein the transparent conductive substrate is a transparent plastic substrate formed with a transparent conductive film.
  3.   The method for producing a photoelectric conversion element according to claim 1, wherein a temperature equal to or lower than a softening temperature of the transparent conductive substrate is 50 ° C. or higher.
  4.   The method for producing a photoelectric conversion element according to claim 1, wherein a temperature not higher than a softening temperature of the transparent conductive substrate is 200 ° C. or lower.
  5.   The method for producing a photoelectric conversion element according to claim 1, wherein a temperature not higher than a softening temperature of the transparent conductive substrate is 50 ° C. or higher and 120 ° C. or lower.
  6.   The method for producing a photoelectric conversion element according to claim 1, wherein a sensitizing dye is previously supported on the semiconductor fine particles dispersed in the paste.
  7.   The method for producing a photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is a wet solar cell.
  8. A paste containing semiconductor fine particles carrying a sensitizing dye and containing a binder is applied onto a transparent conductive substrate,
    After the paste is dried at a temperature equal to or lower than the boiling point of the solvent contained in the paste to remove the solvent, 30 ° C. or higher, which is the lower of the softening temperature of the transparent conductive substrate and the deactivation temperature of the sensitizing dye A method for manufacturing a photoelectric conversion element, wherein the semiconductor fine particles are pressed onto the transparent conductive substrate by pressing the paste while being heated to a temperature equal to or lower than that temperature to form a semiconductor electrode composed of the semiconductor fine particles. .
  9. The method for producing a photoelectric conversion element according to claim 8, wherein the photoelectric conversion element is a dye-sensitized wet solar cell.
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